Silver halide color photographic materials containing a 3-ureido-5-pyrazolone coupler and an aldehyde compound

ABSTRACT

Color photographic materials forming magenta dye images of excellent heat and moisture resistance comprising a support having a silver halide photographic emulsion layer containing a 3-ureido-5-pyrazolone magenta coupler together with a compound having an aldehyde group bonded to a carbon atom.

United States Patent [191 Hara et al.

[451 Jan. 21, 1975 1 SILVER HALIDE COLOR PI-IOTOGRAPHIC MATERIALSCONTAINING A 3-UREIDO-5-PYRAZOLONE COUPLER AND AN ALDEHYDE COMPOUND [75]Inventors: Hiroshi Hara; Yukio Yokota;

IIiroyuki Amano; Tokio Nishimura, all of Kanagawa, Japan [73] Assignee:Fuji Photo Film Co., Ltd.,

Kanagawa, Japan [22] Filed: May 31, 1973 [21] Appl. No.: 365,678

[30] Foreign Application Priority Data May 31, 1972 Japan 47-54500 [52]US. Cl 96/100, 96/56, 96/74,

96/111 [51] Int. Cl G03c 1/40 [58] Field of Search 96/100, 56, 111

[56] References Cited UNITED STATES PATENTS 2,518,686 8/1950 Harsh etal. 96/56 3,140,177 7/1964 Welch 96/56 3,393,071 7/1968 Monbaliu et al 196/100 3,468,666 9/1969 Shiba et al 4 96/100 3,558,319 l/197l Hamaoka etal Jo/100 OTHER PUBLICATIONS Croome et al., Photographic Gelatin, page18, Focal Press, N.Y., 1965.

Primary Examiner-J. Travis Brown Attorney, Agent, or Firm-Sughrue,Rothwell, Mion, Zinn & Macpeak [57] ABSTRACT 21 Claims, N0 DrawingsSILVER IIALIDE COLOR PHOTOGRAPHIC MATERIALS CONTAINING AS-UREIDO-S-PYRAZOLONE COUPLER AND AN ALDEHYDE COMPOUND BACKGROUND OF THEINVENTION 1, Field of the Invention The present invention relates tocolor photography, more particularly, it relates to a color photographicmaterial capable of forming magenta dye images of good heat and moistureresistance.

2. Description of the Prior Art It is well known in the field of colorphotography that cyan, magenta and yellow color images are formed by thecoupling of the oxidation product of an aromatic primary aminodeveloping agent and color forming couplers. It is also known thatvarious pyrazolone derivatives can be used for forming magenta colorimages.

The magenta dye images are ordinarily unstable to heat and moisture, andwhen they are exposed to heat or moisture or are stored for a longperiod of time, the low density portions of the magenta dye images tendto fade. It is known that such a phenomenon occurs due to unreactedcoupler remaining in the color photographic material, and, thus, theaforesaid tendency is particularly seen at low density image portionswhere a large amount of unreacted coupler remains (see, e.g., P. W.Vittum; Journal of the American Chemical Society; Vol. 72, 1533(1950)).

Various methods for preventing fading of magenta dye images have beenproposed. For instance, according to the method described in US. Pat.No. 3,140,177, a color photographic material is processed in an acidprocessing solution containing formalin as the final processing step ofthe color photographic material. However, such a method is undesirablesince formalin gives off a bad odor and further it can be harmful to thebody.

According to US. Pat. No. 3,468,666, a bispyrazolone prepared by thecondensation of 3-acylamino-5- pyrazolone and an aldehyde is used as themagenta coupler. However, such a bispyrazolone has the fault that itdoes not give a sufficient coupling density upon color development.Furthermore, the dye image formed by such a bispyrazolone is not veryfast to heat and moisture.

Accordingly, the development of new means for forming magenta dye imagesof good fastness to heat and moisture has been desired.

SUMMARY OF THE INVENTION One object of this invention is, therefore, toprovide a color photographic material capable of forming fast magentaimages.

It has been discovered that the above mentioned object of this inventioncan be attained by using a 3- ureido-S-pyrazolone and a compound havingan aldehyde group bonded to a carbon atom. Thus, according to thepresent invention, a silver halide photographic emulsion containing a3-ureido-5-pyrazolone type magenta coupler and a compound having analdehyde group bonded to a carbon atom is presented.

DETAILED DESCRIPTION OF THE INVENTION According to one embodiment ofthis invention, there is provided a color photographic material com- H o(l) wherein R, represents an alkyl group or an aryl group and Rrepresents a phenyl group and at least one of a compound having analdehyde group bonded to a carbom atom.

The term non-diffusible" in this specification has its well knownmeaning as it is used for color couplers in the field of colorphotography, i.e., it means that the coupler does not substantially movein the colloid layers of a photographic material in the presence of anaqueous alkaline processing solution.

When R, represents an alkyl group, most generally the alkyl group willhave 1 to 32 carbon atoms, though this range is not limitative. It ismost preferred that when R, is an alkyl group it have 8 to 18 carbonatoms, since an alkyl group with 8 or more carbon atoms acts as aballasting group, while alkyl groups of 19 or more carbon atoms are notpreferred from an industrial stand point, i.e., the compounds have anincreased production cost, difficulty of synthesis, etc.

When R, is an aryl group, it is monoaryl as exemplified in the followingparagraphs.

When R represents a substituted phenyl group, preferred substituentsinclude halogen, cyano, nitro, alkyl of 1-18 carbon atoms, alkoxy ofl-l8 carbon atoms, aryl, e.g., phenyl, tolyl, etc., aryloxy, e.g.,phenoxy, etc., carbamoyl, sulphamoyl, sulphonamido or acyl.

Specific examples of R include phenyl, 2- chlorophenyl, 4-chlorophenyl,2,5-dichlorophenyl, 2,6- dichlorophenyl, 2,4,6-trichlorophenyl,2-bromophenyl, 3,5-dibromophenyl, 2-cyanophenyl, 3-nitrophenyl, 4-methylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 4-butylphenyl,2-trifluoromethylphenyl, 2- ethoxyphenyl, 4-phenylphenyl,4-phenoxyphenyl, N- methylbenzamidophenyl, N,N-diphenylcarbamoylphenyl,N,N-dibutylsulfamoylphenyl, N,N-diphenylsulfamoylphenyl,N-methylsulfonamidophenyl, Z-methyl- 5-nitrophenyl,2-chloro-5-cyanophenyl, 5-chloro-2- methylphenyl,2,6-dichloro-4-methylphenyl, 2,4-dichloro--methylphenyl, 2-chloro-4,6-dimethylphenyl, 2,6-dichloro-4methoxyphenyl, 2,6-dichloro-4-nitrophenyl, 2,4,6-trimethyl 3-nitrophenyl,2,4,6-trimethyl-3-acetamidophenyl, 2,4,6-trimethyl-3-[a-(2,4-di-tert-amylphenoxy)butylamido]phenyl and the like.

Among the 3-ureido-5-pyrazolones represented by general formula I, thecouplers of the formula in which at least one orthoposition of thephenyl group represented-by R has been substituted by a halogen atom, analkyl group having l-5 carbon atoms, or an alkoxyl group having 1-5carbon atoms is particularly preferred.

Specific examples of the group R, of general formula I include alkylgroups such as methyl, ethyl, propyl, isopropyl, butyl, iso-butyl,tert-butyl, amyl, hexyl. octyl, decyl, dodecyl, pentadecyl, octadecyl,allyl. heptadecenyl, and benzyl groups, and aryl groups such as phenylCOOR and tolyl groups. 11

The phenyl groups having the following substituents are used as thegroup R, of general formula I; -OR

In the above formulae, R R R R R R and R H R each represents an alkylgroup; R R and R each rep- 5 resents a hydrogen atom or an alkyl group;and n is an integer of 1-5. Generally, any alkyl group for the moi- R 5eties R to R listed above will have from 1 to 18 car- -NHCO CH bonatoms, and for practical purposes are preferably I unsubstituted.

It is preferred that at least one of R and R of general formula 1 have aballast group making the coupler nondiffusible. As is known in the art,ballast groups are hydrophobic groups usually containing 8 to 32 carbonatoms.

Examples are described in US. Pat. Nos. 2,600,788; 2,865,751; 3,337,344and 3,418,129, and Japanese Patent Publications 27563/64 and 19035/70.

Specific examples of the 3-ureido-5-pyrazolone cou- 10 plers areillustrated below:

cor -NhCoCll Cn Iv R Coupler l N110 lH-C-CH tert C 11 Ol H l 2 Coupler 2OCH CONE sec .li ll 2 Coupler El nncom-c CH n i 2 c n ooc N\ c=o Coupler22 A u -NHO tert. i1 0(c s NllCONH (I slu ll e=o tert.(l ll I? Coupler25 -l 3l-lCONH 0- on n 2 C=O 12 2' \N/ Coupler 2L1 OCHCONHQNHCONH c- H22, H inf =0 The 3-ureido-5pyrazolor e couplers used in this in.- ventioncan be prepared according to the methods described in US. Pat. No.3,558,319; and Japanese Patent Applications 100911/1970; 106716/1970,etc.

In the silver halide emulsion of thisinvei tion, the abovementioned3-ureido-5-pyrazolone couplers can be used alone or as a combination oftwo or more couplers. Furthermore, the 3-ureido-5-pyrazolor e couplermay be used together with other two-equivalent or four-equivalentcouplers. These couplers are sometimes called colorless couplers,colored couplers or DlR couplers, and specific examples of them includethe couplers described in US. Pat. Nos. 2,455,170; 2,600;7,88;2,908,573; 3,062,653; 3,148,062;

3,227,551; 3,227,554; 3,519,429; and 3,617,291.

The 3-ureido-5-pyrazolene couplers of the present invention, whetherused singly or as a combination of two or more thereof, are notparticularly limited in proportions so long as the objects of thepresent invention are met. However, generally speaking, they will beused in an amount of from about to about 100 percent by weight,preferably 50 to 100 percent by weight, of the total amount of magentacolor forming couplers used.

Those color couplers are introduced into a hydrophilic colloid as istypically used for photographic materials according to any known method.For instance, they can be dispersed in a hydrophilic colloid using ahigh boiling point organic solvent such as dibutyl phthalate andtricresyl phosphate as described in U.S. Pat. No. 2,322,027 and/or alow-boiling point organic solvent such as ethyl acetate andtetrahydrofuran as described in U.S. Pat. Nos. 2,801,170; 2,801,171; and2,946,360.

The aldehydes used together with the 3-ureido-5- pyrazolone coupleraccording to the present invention include compounds having an alkylgroup, an aryl group, or a heterocyclic group bonded to the aldehydegroup, i.e., aliphatic aldehydes, aromatic aldehydes or heterocyclicaldehydes can be used in the present invention. The aliphatic aldehydespreferably contain from 2 to 20 carbon atoms, most preferably 2 to 8carbon atoms. Among the aromatic aldehydes, most preferred are thosecontaining a formyl group attached to the phenyl or naphthyl ring,though aryl substituted with halogen, nitro, hydroxy, C -C alkyl, C,Calkoxy ally], carboxy, sulpho and the like are also useful.

Among the aldehydes, benzaldehydes with or without the abovesubstituents are preferred.

Specific examples of such compounds are acetaldehyde, propionaldehyde,butylaldehyde, isobutylaldehyde, pivalylaldehyde, heptaldehyde, laurinaldehyde, stearinaldehyde, succindialdehyde, crotonaldehyde,benzaldehyde, o-chlorobenzaldehyde, mchlorobenzaldehyde,p-chlorobenzaldehyde, pbromobenzaldehyde, p-nitrobenzaldehyde, p-

hydroxybenzaldehyde, o tolualdehyde, cinnamaldehyde, a-naphthaldehydeand furfural, etc.

Those aldehydes can be used alone or as a combination of two or more ofsuch aldehydes. The addition amount of the aldehyde is usually about0.05 to about mols, in particular about 0.1 mol to about 10 mols, permol of the coupler.

It is preferred that the aldehyde be added to a hydrophilic colloid whenpreparing the coupler dispersion by adding the abovedescribed coupler orcouplers to the hydrophilic colloid together with the aforesaid highboiling point organic solvent and/or the low boiling point organicsolvent. Alternatively, they can be added to a silver halide emulsion atthe preparation of coating compositions together with the couplerdispersion, a hardening agent, a stabilizer, a wetting agent, etc.

The amount of magenta forming coupler in accordance with the presentinvention is not limited so long as, of course, the color photographicmaterial of the present invention meets the objects heretofore recited,that is, yields a magenta dye image of good heat and moistureresistance. However, since commercially it is necessary to provide anelement which will provide results pleasing to the vast majority ofpurchasers, generally the amount of magenta color forming coupler willbe from about 0.05 to about 0.5 moles per mole of silver halide, mostpreferably, 0.07 to 0.2 moles per mole of silver halide.

Any known hydrophilic colloid(s) as are used in the color photographicart can be used as the hydrophilic colloid for the silver halidephotographic emulsion layer of this invention. Preferred examples ofsuch hydrophilic colloids are gelatin, albumin, gum arabic. agar agar,cellulose derivatives (such as alkyl esters of carboxymethyl cellulose,hydroxyethyl cellulose, carboxymethyl hydroxyethyl cellulose, etc.), andsynthetic resins (such as polyvinyl alcohol, polyvinyl pyrrolidone,etc.). These hydrophilic colloids are also preferably used as thebinders for layers of the photographic material other than the silverhalide emulsion layers, such as a protective layer, a filter layer, anintermediate layer, an antihalation layer, a subbing layer, a backinglayer, etc.

The hydrophilic colloids used in various layers of the photographicmaterial of this invention can be effectively hardened by hardeningagents such as 1,4- dioxanes, aziridines, iso-oxazoles, active halogens,active vinyl compounds, etc. Typical examples of such hardening agentsare described in U.S. Pat. Nos.

3,100,704; 3,091,537; 3,321,313 and 3,543,292 and British Pat. Nos.974,723; 1,167,207 and 994,869.

In the present invention any silver halide emulsion as is usually usedin the field of photography, such as a silver bromide emulsion, silveriodobromide emulsion, silver chloroiodobromide emulsion, silverchlorobromide emulsion and silver chloride emulsion can be used. Also,the so-called converted halide type silver halide emulsions as describedin, e.g., U.S. Pat. No. 3,622,318 and British Pat. No. 635,841, can beused. A preferred average gain size for the silver halide is from about0.05 to about 1.5 microns. The weight ratio of silver halide to bindermost suitably ranges from about 0.2 to about 20 (silver halide/binder),preferably about 0.3 to about 5 in the layer. These values are notlimitative, but provide a most superior element.

The silver halide emulsions (used in the color photographic materials)of this invention can be chemically sensitized by active gelatin or asulfur compound according to the process described in U.S. Pat. Nos.1,574,944; 1,623,499 and 2,410,869. They can also be sensitized by anoble metal salt such as a palladium or a gold salt as described in U.S.Pat. Nos. 2,448,060; 2,399,083 and 2,642,361. Furthermore, they can besensitized by a reducing agent such as a stannous salt as described inU.S. Pat. No. 2,487,850, or sensitized by a polyalkylene derivative.They can also be spectrally sensitized by a cyanine by or merocyaninedye such as described in U.S. Pat. Nos. 2,519,001; 2,666,761; 2,734,900;2,739,964 and 3,481,742.

The silver halide emulsion of this invention can contain a stabilizersuch as a mercury compound, mercaptotetrazole, thiazole, azaindene,etc.; a plasticizer such as glycerin, latex, etc.; and a wetting agentsuch as saponin, polyethylene glycol monolauryl ether, etc. Furthermore,the silver halide emulsion can contain an antistatic agent, anultraviolet absorbent, a fluorescent whitening agent, dyes, etc.

The silver halide emulsion containing the 3-ureido-5- pyrazolone and thealdehyde compound according to this invention is effectively used as agreen-sensitive emulsion layer in an ordinary multi-layer colorphotographic material. ln this case, the order of the photosensitiveemulsion layers may be, from the support side, a red-sensitive emulsionlayer, a green-sensitive emulsion layer and a blue-sensitive emulsionlayer, or may be a blue-sensitive emulsion layer, red-sensitive emulsionlayer and a green-sensitive emulsion layer.

In addition to these photosensitive emulsion layers, the colorphotographic material of this invention can have an antihalation layer,intermediate layer(s), filter layer, protective layer, etc.

The support for the photographic materials of this invention on whichthe photosensitive silver halide emulsion layers are formed ispreferably a cellulose ester film such as a cellulose nitrate film, acellulose acetate film, etc.; a polyester film such as a polyethyleneterephthalate film; a polyvinyl chloride film; a polystyrene film; apolycarbonate film; a baryta-coated paper; a resin-coated paper, and thelike. This listing is, of course, not limitative.

The color photographic material of this invention is imagewise exposedin an ordinary way and then processed according to usual colorphotographic processings. The main processing steps are a colordevelopment, a bleach and a fix and, if necessary, a washing step may beapplied between each step. After fixing, the color photographic materialis washed and dried but it is desirable to process the colorphotographic material in a stabilization bath prior to drying.

As is known to those skilled in the art, photographic processingtemperatures typically range from about C or less to 60C or higher.Temperatures of about 30C or higher are suitable for high speedprocessing procedures. Processing times for each processing step canvary widely, depending on the processing temperature, but usually rangefrom several seconds to several minutes or more.

Useful color developers are aqueous alkaline solutions containing acolor developing agent. As the color developing agent, all known primaryaromatic amine dye-forming developing agents can be used. Examples ofsuch color developing agents are phenylenediamines such as N,N-diethylp-phenylenediamine, N-ethylhydroxyethyl p-phenylenediamine, N-ethyl-N-hydroxyethyl-2-methyl p-phenylenediamine, N-ethyl- B-N-methanesulfoneamidoethyl-3-methyl-4- aminoaniline,N,N-diethyl-2-methyl-pphenylenediamine, and sulfates, hydrochlorides,sulfides, etc., thereof. See C. E. K. Mees and T. H. James, The Theoryof the Photographic Process, pages 294295 (The Macmillan Co., 1966), andU.S. Pat. Nos. 2,592,364 and 2,193,015. The color developer used fordeveloping the color photographic material of this invention may furthercontain ordinary additives as are used in this art such as a sulfite ofan alkali metal, a carbonate, a bisulfite, a bromide, an iodide, benzylalcohol, etc.

The bleach solution can contain any known bleaching agent such asferricyanide, bichromate, etc. Also, the fix solution can contain anyknown fixing agent such as sodium thiosulfate, potassium thiocyanate,etc. Furthermore, the bleach step and the fix step can be conducted inone bath, and such a blix bath is described in, e.g., U.S. Pat. No.3,582,322.

Typical bleach agents are discussed in detail in the Journal of theSociety of Motion Picture and Television Engineers 61, 667-701 and U.S.Pat. No. 3,189,452; typical fix agents in Mason, Photographic ProcessingChemistry, pages 187-188, Focal Press (1966); and typical blix solutionsin German Pat. Nos. 866,605 and 966,410, in British Journal ofPhotography, pages 122123 and 126 (1966) and in U.S. Pat. No. 3,582,322.These references also discloses generally used proportions.

The photographic material of this invention provides stable color imageswhich are not faded if the photographic material is exposed to heat ormoisture or stored for a long period of time. This merit is obtained bythe combination of the 3-ureido-5-pyrazolonc and the aldehyde asmentioned above without using formulin, i.e., since the aldehydes of thepresent invention are limited to those having an aldehyde group bondedto a carbon atom, formaldehyde is excluded from the scope of the presentinvention. This is quite astonishing upon considering that if theaforesaid aldehyde is used together with 3-acylamino-5-pyrazolone, thestability of the color images cannot be improved.

Furthermore, the aldehyde used in this invention does not have a harmfulinfluence on the photographic properties, e.g., hindering the couplingof couplers and causing stain as in the case of using formalin or acompound releasing formalin.

Moreover, the aldehyde in this invention has the effect of preventingthe formation of magenta development fog. Further, changes insensitivity of the photosensitive emulsion of this invention duringstorage is prevented. This effect is further observed in the emulsionlayers formed over or under the silver halide emulsion layer of thisinvention, and is a surprisingly effect.

The invention will now be explained in further detail by the followingexamples.

EXAMPLE 1 Coupler dispersion A B C D Coupler l g 100 g 100 g (earlierset out) Coupler A (known) 100 g Dibutyl phthalate 100 g 100 g I00 g 100g Ethyl acetate 200 g 200 g 200 g 200 g 10% aqueous gelatin 1000 g 1000g 1000 g 1000 g solution Aqueous solution of 50 g 50 g 50 g 50 g 5%sodium dodecylbenzene sulfonate Acetaldehyde 6 g Heptaldehyde 5 g Knowncoupler A: the condensation product of 1-phenyl-3-[3-(2-carboxymethyleicos-3-enamide)-benzamido]-5-pyrazolone andacetaldehyde described in U.S. Pat. No. 3,468,666.

Each of the samples thus prepared was stagewise exposed (1,000 lux, 1sec.) through a green filter transmitting light of 500-600 mg and asilver wedge and then processed as follows:

TABLE 1 Sample Maximum Dye remaining percentage density initial initialProcessing step temperature time 5 d ity 5 d nsity 1.5

Color development 30C 4 min. A 2.5 45 60 Blix 30C 2 min. B 2.5 85 90Washing 30C 2 min. c 2.5 87 90 Stabilization 30C 2 min. 1) 1,7 55 65Sample B and C containing the 3-ureido-5- The compositions of theprocessing solutions used in Pyralolone Coupler and the aldehydeacFordmg to {1115 the processings wme as Shown below; invention gavestable magenta dye images which caused less fading, and this tendencywas particularly remarkable at the low density portions. On the otherColor developer hand, Sample D containing the known coupler gaveinsodium metaborate 25 g sufficient coupling density and gave unstabledye M- sodium sulfite 2 g ages hydroxylamine (sulfate) 2 g potassiumbromide 0.5 g 6-nitrobenzimidazole (nitrate) 0.02 g sodium hydroxide 4 gEXAMPLE 2 benzyl alcohol l5.8 ml dNiethhylprltle glycol 20 ml A subbinglayer was formed on a cellulose acetate -et y- -B-(methanesulfone- 8 gamidoelhyl) p phenylenediamine fllm support having an antlhalatlon layercontain ng water to make 1000 ml carbon black on the opposlte slde, andthen a coating composition containing a silver iodobromide emulsion lronsalt of ethylenedlamlne- 45 g mimetic acid containing 1.2 mol percentiodine and a coupler disperan moniun l thiocyanate {8g sion prepared bydispersing a yellow coupler, a-(2- so lum su lte 8 ammonium thiosulfate(60%) 100 ml methylbenzoyl)-3-[a:( 2,4-dl:tert-amylphenoxtetrasodiumethylenediamine- 5g y)acetamldo]-acetanlllde uslng dlbutyl phthalate andemacelate ethyl acetate was coated on the subbing layer to form water tomake 1000 ml. Stabilizing bath; a blue-sensitive layer. A gelatinintermediate layer was "F acid 10 2; formed on the blue-sensitive layerand a coating comzlnc sulfate 10 g Sodium member 20 g posltloncontaining a gelatlno silver chlorobromlde water to make 1000 ml.emulsion containing 30 mol percent bromide and spectrally sensitized sothat it had its sensitization maximum at about 685 mg, and a couplerdispersion prepared by After measuring the reflection density of themagenta dispersing a cyan coupler, l-hydroxy-4-chloro-N- dye images thusformed, the processed samples werehexadecyl-N-(2-cyanoethyl)-2-naphthamide using stored for 14 days at 60Cand 70 percent relative hu- 4O butyl phthalate and ethyl acetate wascoated on the inmidity to conduct a fading test and then the reflectiontermediate layer to form a red-sensitive layer. A gelatin density of thedye images was again measured. The perintermediate layer was coated onthe red-sensitive layer centage of dye remaining in the portions havingimage and then a coating composition containing 100 g of sildensities of0.5 and 1.5 before the fading test were calver chlorobromide (containing0.06 mol of silver) conculated by the following equation and are shownin taining 35 mol percent bromide and spectrally sensi- Table l. tizedso that it had its sensitization maximum at about 555 mg, and 250 g ofacoupler dispersion prepared by Dye rema ng Pe ce tage X 100 dispersingthe following components by means of a ho- A. dye denslty after fadingtest fOg dens y af e mogenizer was coated on the intermediate layer tofadlng test. form a green-sensitive layer. A gelatin protective layer B:dye denslty before fading test-fog denslty before was at d on th m lsilayer, Samples E-I were fadlng {L thus prepared. All systems weregelatino systems.

Coupler dispersion E F G H l Coupler I0 50 g 50 g 50 g 50 g (earlierdescribed) Known coupler B 50 g 50 g 50 g 50 g g Dibutyl phthalate 50 g50 g 50 g 50 g 50 g Ethyl acetate 200 g 200 g 200 g 200 g 200 g l0% aq.gelatin l000 g 1000 g 1000 g 1000 g 1000 g solution aq. solution of 571100 g I00 g 100 g 100 g I00 g sodium dodecylbenzene sulfonateBenzaldehyde 3 g p-Chlorobenzaldehyde 4 g 4 g p-Nitrohenzaldehyde 4 gKnown coupler B: l-(2,4,6trichlorophenyl)-3 3- say, it will beunderstood that the use of the aldehyde-di-tert-amylphenoxy)butylamido]benzamido in this invention was onlyeffective in the combination S-pyrazolone. with the3-ureido-5-pyrazolone.

Each of the samples was exposed as in Example 1 and subjected to thefollowing processings:

EXAMPLE 3 Processing step On the surface of a paper, both surfaces ofwhich te mperature time PIC-Processing bath 2d7C sec were laminated withpolyethylene containing titanium Washing 0. l5 sec. (Mm development 5 mmSam 10 dioxide, a coating composition containing a silver chlo Washingdo. i5 5% robromide containing 85 mol percent of bromine and 4 l acoupler dispersion prepared by dispersing a yellow Washing do 2 min.

mammalian do, 10 Sec coupler,a-(4-methoxybenzy1)-3-[a-(2,4-di-tertamylphenoxybutylamide)]-6-chloroacetoanilide,using dibutyl phthalate and ethyl acetate, was coated to form ablue-sensitive layer. A gelatin intermediate layer was formed on theblue-sensitive layer. On the intermediate layer, a coating compositioncontaining 100 g of silver sg l bath: 800 m] chlorobromide emulsion(containing 0.07 mol of silsodium carbonate (monohydrate) l0 g 20 ver)containing 30 mol percent bromine and 100 g of The compositions of theprocessing solutions used in the steps were as follows:

2-amino-S-diethylaminotoluene hydrochloride (anhydrous) gg I a couplerdispersion prepared by dispersing a sensitizwater 0 ma e m a Colo,developer; mg dye having its sensitization maximum at about 545 Water800 ml my. and the components shown below by means of a sodiumhexametaphosphate 2 g anhydrous Sodium Sulfite 4 g homogenizer wascoated in a coated silver amount of l X 10 mol/m 3 g sodium carbonate(monohydrate) 2.5 g potassium bromide 2 0 g water to make 1000 ml Blixsolution:

sodium iron(lll) ethylene- 34 g Coupler dlsperslon J K L Mdiaminetetraacetic acid sodium carbonate (monohydrate) ll g Egg}; g g gg borax 45 g Dibutyl phthalate 100 g l00 g 100 g I00 g fff fl gig 63% iEthyl acetate 150 g 150 g 150 g I50 g 5 l0% Aqueous 1000 g 1000 g l000 gI000 g tabilization bath. I I

water 800 ml T 5 polyethylene glycol (MWAOO) 5 ml z gmgz a s g y g g I40% aqueous solution h M h d 5 water to make 1000 ml. enza e y e g Aftermeasuring the transmission density of the magenta dye images thusformed, the processed samples were stored for 30 days at 50C and 70%relative hu- 40 midity and then the transmission density of the dyeimages was again measured. The dye remaining percentages of the portionshaving image densities of 0.5 and 2.0 before the fading test are shownin Table 2, with all values being calculated as in Example 1.

A gelatin intermediate layer containing an ultraviolet absorbent,2-(2'-hydroxy-3'-methyl-5'-sec-butylphenyl)benzotriazole, was coated onthe emulsion layer and further, on the intermediate layer, a coatingcomposition containing silver chlorobromide containing 40 mol percentbromine and a coupler dispersion prepared by dispersing a cyan coupler,4,6-dichloro-3- methyl-2-[0z-(2,4-di-tertamylphenoxy)acetamido1phenol,using dibutyl phthalate and ethyl acetate, was coated. Finally, agelatin pro- TABLE 2 Sample Fog Dye remaining percentage tective layerwas coated on the emulsion layer. Samples density initial initialJ-llwerp thit s prekpared. f h 1 d irecty a ter t e preparation 0 t esamp es an dens), density after storing the samples for 3 days at 40Cand 80% E 0.08 50 70 relative humidity, the samples were wedge exposed g338; 3 using a filter transmitting light of 500600 mu and a fillil 8.8g:2 3 3 ter transmitting light have wave lengths longer than 600 mu, andthen processed as in Example 1. The red sensitivity and the greensensitivity of the various samples thus processed were measured, andfrom the results the From the above results, it will be understood thatin change in sensitivity with the storage under highsamples F, G, and Hof this invention, stable magenta temperature and high-humidityconditions was deterdyes causing less fading of dye images wereobtained, mined. The results are shown in Table 3, in which the andfurther the occurence of magenta development fog value 0.30 shows thatthe sensitivity of the sample was suppressed. On the other hand, in thecomparsion measured was reduced by 0.30 (in logarithmic units) as sampleI in which the 3-acylamino-5-pyrazolone ma- 5 compared with thesensitivity of the fresh sample. Also, genta coupler and the aldehyde ofthis invention were the fog density and the results of a fading testconused, the fading of the dye image was great. That is to ducted as inExample 1 are shown in the same table.

TABLE 3 Sample Change of sensitivity Fog Dye remaining percent Red sens.Green sens density initial initial density density M 0. l 5 0,5() 0.1 l90 95 From the above results, it will be understood that the stabilityof the magenta images was improved by this invention, and further thefog density of the magenta layer was lowered and the change of thesensitivity of the green-sensitive layer itself, as well as thesensitivity of the red-sensitive layer were minimized by this inventionwhen the samples of this invention were stored under high temperatureand high-humidity conditions.

Thus, the excellent points of the color photographic materials of thisinvention will be understood from the above examples.

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What we claim is:

l. A color photographic material which provides magenta dye images ofexcellent heat and moisture resistance and reduced magenta developmentfor comprising a support having thereon a silver halide photographicemulsion layer containing a 3-ureido-5- pyrazolone magenta coupler and acompound having an aldehyde group bonded to a carbon atom;

wherein said magenta coupler is a compound represented by the formulawherein R, represents an alkyl group or an aryl group and R represents aphenyl group; and

wherein said aldehyde group is bonded to the carbon atom of an alkylgroup, an aryl group or a furfural group, wherein said alkyl groupcontains from 2-20 carbon atoms and said aromatic group is aformylsubstituted phenyl or naphthyl ring. 2. A color photographicmaterial as set forth in claim I wherein R, is a C,C carbon atom alkylgroup or a monoaryl group and R is a phenyl group.

3. A color photographic material as set forth in claim 2 wherein R, is aC,,C,,, carbon atom alkyl group, a phenyl group or a tolyl group.

4. A color photographic material as set forth in claim 1 wherein R is aphenyl group substituted with a halogen atom, a C,C alkyl group or a C,Calkoxyl group.

5. The color photographic material as set forth in claim 1 wherein atleast one of R, and R has a ballast group.

6. A color photographic material as set forth in claim 5 wherein theballast group is a C -C hydrophobic group.

7. A color photographic material as set forth in claim 1 wherein theamount of magenta dye-forming coupler is from about 0.05 to about 0.5moles per mole of silver halide in the emulsion.

8. A color photographic material as set forth in claim 7 wherein theamount of magenta dye-forming coupler is from about 0.07 to about 0.2moles per mole of silver halide in the emulsion.

9. The color photographic material as set forth in claim 7 wherein theproportion of said compound having an aldehyde group bonded to a carbonatom is from 0.05 mol to about 30 mols per mol of said magenta coupler.

10. A color photographic material as set forth in claim 1 wherein thealkyl group bonded to a carbon atom contains from 2 to 20 carbon atoms,and the aromatic group bonded to a carbon atom is a formylsubstitutedphenyl or naphthyl ring.

11. A color photographic material as set forth in claim 1, wherein saidaryl group bonded to said aldehyde group is substituted with halogen,nitro, hydroxy, C, C alkyl, C C alkoxy, aryl, carboxy or sulfo.

12. A color photographic material as set forth in claim 1 wherein thealdehyde is a benzaldehyde.

13. A color photographic material as set forth in claim 12 wherein thebenzaldehyde is substituted with halogen, nitro, hydroxy, C,C,, alkyl,C,C alkoxy, aryl, carboxy or sulfo.

14. A color photographic material as set forth in claim 1 where thecompound having an aldehyde group selected from the group consisting ofacetaldehyde,

propionaldehyde, butylaldehyde, isobutylaldehyde, pivalylaldehyde,heptaldehyde, laurinaldehyde, stearinaldehyde, succindialdehyde,crotonaldehyde, benzaldehyde, ochlorobenzaldehyde, m-chlorobenzaldehyde,pchlorobenzaldehyde, p-bromobenzaldehyde, pnitrobenzaldehyde,p-hydroxybenzaldehyde, o-

tolualdehyde, cinnamaldehyde, a-naphthaldehyde or furfural.

15. A color photographic material as set forth in claim 14 wherein theaverage grain size of the silver halide present in the emulsion is fromabout 0.05 to about 1.5 microns.

16. A color photographic material as set forth in claim 15 wherein theweight ratio of silver halide to binder is from about 0.2 to about 20(silver halidebinder).

17. A color photographic material as set forth in claim 1 wherein R, isan alkyl group.

18. A color photographic material as set forth in claim 1 wherein R, isan aryl group.

19. A color photographic material as set forth in claim 1 wherein R, isa phenyl group selected from:

(a) NllCOlt (b) NHCO COR 1/ 9 ((1) b I:

(e) -0oon,

, wherein R R R R R R and R each represent an alkyl group, and n is aninteger of 1-5.

20. A color photographic material as set forth in claim 19 wherein anyof R -R has from 1 to 18 carbon atoms.

2. A color photographic material as set forth in claim 1 wherein R1 is aC1-C32 carbon atom alkyl group or a monoaryl group and R2 is a phenylgroup.
 3. A color photographic material as set forth in claim 2 whereinR1 is a C8-C18 carbon atom alkyl group, a phenyl group or a tolyl group.4. A color photographic material as set forth in claim 1 wherein R2 is aphenyl group substituted with a halogen atom, a C1-C5 alkyl group or aC1-C5 alkoxyl group.
 5. The color photographic material as set forth inclaim 1 wherein at least one of R1 and R2 has a ballast group.
 6. Acolor photographic material as set forth in claim 5 wherein the ballastgroup is a C8-C32 hydrophobic group.
 7. A color photographic material asset forth in claim 1 wherein the amount of magenta dye-forming coupleris from about 0.05 to about 0.5 moles per mole of silver halide in theemulsion.
 8. A color photographic material as set forth in claim 7wherein the amount of magenta dye-forming coupler is from about 0.07 toabout 0.2 moles per mole of silver halide in the emulsion.
 9. The colorphotographic material as set forth in claim 7 wherein the proportion ofsaid compound having an aldehyde group bonded to a carbon atom is from0.05 mol to about 30 mols per mol of said magenta coupler.
 10. A colorphotographic material as set forth in claim 1 wherein the alkyl groupbonded to a carbon atom contains from 2 to 20 carbon atoms, and thearomatic group bonded to a carbon atom is a formyl-substituted phenyl ornaphthyl ring.
 11. A color photographic material as set forth in claim1, wherein said aryl group bonded to said aldehyde group is substitutedwith halogen, nitro, hydroxy, C1 - C8 alkyl, C1 - C8 alkoxy, aryl,carboxy or sulfo.
 12. A color photographic material as set forth inclaim 1 wherein the aldehyde is a benzaldehyde.
 13. A color photographicmaterial as set forth in claim 12 wherein the benzaldehyde issubstituted with halogen, nitro, hydroxy, C1-C8 alkyl, C1-C8 alkoxy,aryl, carboxy or sulfo.
 14. A color photographic material as set forthin claim 1 where the compound having an aldehyde group is selected fromthe group consisting of acetaldehyde, propionaldehyde, butylaldehyde,iso-butylaldehyde, pivalylaldehyde, heptaldehyde, laurinaldehyde,stearinaldehyde, succindialdehyde, crotonaldehyde, benzaldehyde,o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde,p-bromobenzaldehyde, p-nitrobenzaldehyde, p-hydroxybenzaldehyde,o-tolualdehyde, cinnamaldehyde, Alpha -naphthaldehyde or furfural.
 15. Acolor photographic material as set forth in claim 14 wherein the averagegrain size of the silver halide present in the emulsion is from about0.05 to about 1.5 microns.
 16. A color photographic material as setforth in claim 15 wherein the weight ratio of silver halide to binder isfrom about 0.2 to about 20 (silver halide-binder).
 17. A colorphotographic material as set forth in claim 1 wherein R1 is an alkylgroup.
 18. A color photographic material as set forth in claim 1 whereinR1 is an aryl group.
 19. A color photographic material as set forth inclaim 1 wherein R1 is a phenyl group selected from:
 20. A colorphotographic material as set forth in claim 19 wherein any of R3-R12 hasfrom 1 to 18 carbon atoms.
 21. A color photographic material as setforth in claim 1 wherein said silver halide photographic emulsion is asilver halide gelatino photographic emulsion, further containing saidmagenta coupler and said compound having an aldehyde group.